JP2009001698A - Redt-emitting phosphor, fed device, and eld device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a red-emitting phosphor of high brightness capable of being used as the red-emitting phosphor of a display apparatus such as FED device and EL device for irradiating the phosphor with an excitation energy source such as an electronic ray and an electric field. <P>SOLUTION: In the red-emitting phosphor, Al (aluminum) and Mn (manganese) are added to a matrix material represented by the general formula: M<SP>II</SP>M<SB>2</SB><SP>III</SP>S<SB>4</SB>and at least one element in the Group IIIa of the periodic table is added as a co-additive wherein M<SP>II</SP>represents one of Mg (magnesium), Ca (calcium), Sr (strontium) and Ba (barium) or a combination of these; and M<SP>III</SP>represents one of Ga (gallium) and In (indium) or a combination of these. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a phosphor used in a display device, a lighting device, and the like, and particularly relates to a red light emitting phosphor. The present invention also relates to an FED device and an ELD device having such a red light emitting phosphor.

  Conventionally, powders or thin film phosphors using rare earth elements have been widely used in the field of display devices such as field emission display (FED) and lighting devices.

In particular, M ^II M ₂ ^III S ₄ (where M ^II is Mg, Ca, Sr, Ba, or a combination thereof, and M ^III is Ga, In, or a combination thereof. Is a base material, and a material obtained by adding a rare earth ion thereto is used as a phosphor for many light emission such as photoluminescence, electroluminescence, and cathodoluminescence. For example, in a phosphor using SrGa ₂ S ₄ and CaGa ₂ S ₄ as a base material, a blue light emitting phosphor that emits light in a blue region (wavelength of about 420 nm to 460 nm) can be obtained by adding Ce ³⁺ ions as an emission center. Can be produced. Further, when Eu ²⁺ ions are added to the above-described base material, a green light-emitting phosphor that emits light in a green region (wavelength of about 530 nm to 570 nm) can be manufactured (for example, Patent Document 1).

On the other hand, as phosphors emitting at a wavelength of about 600 nm to 750 nm, which is a red region, some research has been conducted on BaIn ₂ S ₄ : Eu, CaIn ₂ S ₄ : Eu, SrIn ₂ S ₄ : Eu, and the like. However (Non-Patent Document 1), this material has many problems to be solved such as low emission luminance and poor color purity, and has not been put into practical use at present. Therefore, generally, when obtaining red light emission, phosphors other than M ^II M ₂ ^III S ₄ system such as Y ₂ O ₃ : Eu or CaS: Eu system are used.
JP 2006-124552 A Georgobiani AN, Dzhabbrarov RB, Izzatov BM et al., INORGANIC MATERIALS, 33 (2), p148-152, 1997 Miura, Hidaka, Takizawa, “Emission spectrum of SrGa2S4 with double addition of Mn and Ce”, 67th JSAP Scientific Lecture Proceedings p29-H6, p. 1311

Here, for example, when manufacturing a phosphor for an FED device, it is necessary to emit light of three primary colors, that is, blue, green, and red. Therefore, the M ^II M ₂ ^III S ₄ system material and the others However, such phosphors may have the following problems caused by different base materials.

  In the FED apparatus, since the intensity of the electron beam irradiated to each color phosphor as an excitation energy source is constant, the behavior of charge-up by the electron beam differs between red and other color phosphors. In addition, due to this influence, the balance of light emission of each phosphor is lost, and color adjustment is required between red and other colors in order to maintain color development appropriately. Further, since the base materials are different, the lifetimes of the phosphors of the respective colors are different, and if any one of the phosphors is deteriorated, the apparatus cannot be used even if the characteristics of the remaining phosphors are not deteriorated. Furthermore, the manufacturing process of the phosphor becomes complicated, and the manufacturing cost increases.

Recently, it has been reported that a phosphor obtained by simultaneously adding Ce and Mn ions to a SrGa ₂ S ₄ base material emits red light (Non-patent Document 2). However, the light emission of this material has a peak wavelength in the vicinity of 700 nm. In this region, there is a problem that visibility is extremely low and luminance is low.

In the present invention, in order to solve the problem of color adjustment due to the difference in charge-up, the difference in life and the problem of manufacturing cost as described above, red light emission in which the general formula of the base material is represented by M ^II M ₂ ^III S ₄ It is an object to provide a phosphor. In particular, the red light emitting phosphor according to the present invention can emit light with high luminance in a red region having high visibility. The present invention also provides an FED device and an ELD device using such a red light-emitting phosphor.

In the present invention, M ^II M ₂ ^III S ₄ (where M ^II is any one of Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), or a combination thereof, ^III is a base material represented by Ga (gallium), In (indium), or a combination thereof, and Al (aluminum) and Mn (manganese) are added. There is provided a red light emitting phosphor in which at least one element in Group IIIa is added as a co-additive.

  Here, the co-additive is Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho. It may be at least one of (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), Y (yttrium), Sc (scandium), and La (lanthanum).

In the present invention,
A cold cathode device installed on the cathode layer and having a plurality of electron emitters installed in the opening;
An anode provided with a phosphor layer on the surface facing the cold cathode element;
Have
A field emission display (FED) device in which a phosphor emits light by electrons emitted from the cold cathode device,
The FED device is characterized in that the phosphor layer includes a red light-emitting phosphor as described above.

Furthermore, in the present invention,
An electroluminescent display (ELD) device having an insulating layer on one side or both sides of a phosphor layer and further having electrodes to which a voltage can be applied on both sides of the insulating layer,
An ELD device is provided in which the phosphor layer includes a red light-emitting phosphor as described above.

In the present invention, a red light-emitting phosphor having a general formula of a base material represented by M ^II M ₂ ^III S ₄ and exhibiting high-luminance light emission can be obtained. In addition, it is possible to provide an FED device and an ELD device including such a red light emitting phosphor.

  Hereinafter, the features of the present invention will be described in more detail.

In the present invention, M ^II M ₂ ^III S ₄ (where M ^II is Mg, Ca, Sr, Ba, or a combination thereof, and M ^III is Ga, In, or a combination thereof. A red light-emitting phosphor including a base material, Mn and Al, and a co-additive.

  Here, the term “red light-emitting phosphor” refers to a phosphor that, when excited, has a red color, that is, a peak of emission intensity in a wavelength range of 600 nm to 750 nm.

In general, it is known that Mn does not emit light even when added to a phosphor having M ^II M ₂ ^III S ₄ as a base material. Recently, it has been reported that red light emission can be obtained by adding Mn and Ce to an M ^II M ₂ ^III S ₄ base material, but this phosphor has low visibility. Since light emission occurs only in the region (near the wavelength of 700 nm), there is a problem that luminance is low and practical application is difficult.

On the other hand, the inventors of the present application have good color purity and high color purity in a region where visibility is increased by further adding Al and a co-additive to the M ^II M ₂ ^III S ₄ + Mn system. It was found that bright red light emission was obtained.

  Here, the co-additive is any element located in Group IIIa of the periodic table of elements, or a combination thereof, for example, any one of Sc (scandium), Y (yttrium), and a lanthanoid Or a combination thereof. As lanthanoids, La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium) , Ho (holmium), Er (erbium), Tm (thulium) and Yb (ytterbium).

Note that the clear cause of high-luminance red light emission by adding Mn, Al, and the above-mentioned types of co-additives to the M ^II M ₂ ^III S ₄ system is unknown at present. However, since addition of Mn alone does not cause light emission in the red region, the co-additive is considered to play a role in promoting light emission of Mn which is the emission center of the present material system. For example, when Mn is added to a SrGa ₂ S ₄ matrix material, it is considered that Ga atoms in the phosphor matrix material are replaced with Mn atoms as dopants. However, this substitution alone does not provide an activity enough to emit Mn even when an excitation energy source such as an electron beam is applied. On the other hand, when the above-mentioned co-additive is further added to SrGa ₂ S ₄ , the Sr atom in the host material of the phosphor is replaced with the co-additive atom, and thereby Mn is more easily activated. It is considered to be. Further, when Al is added, an effect of weakening the Mn crystal field is generated, and it is considered that red light emission can be generated in a region where the visibility is high.

  The phosphor according to the present invention can be manufactured, for example, by the following method.

First, M ^II M ₂ ^III S ₄ matrix material powder (where M ^II is Mg, Ca, Sr, Ba, or a combination thereof, and M ^III is either Ga, In, or these A mixed powder of a predetermined amount of Al source powder, a Mn source powder, and a predetermined amount of co-additive source powder. In place of the M ^II M ₂ ^III S ₄ base material powder, powders of sulfides, oxides, carbonates, oxalates, etc. of M ^II and M ^III may be used. The average diameter of the M ^II M ₂ ^III S ₄ base material powder is not particularly limited, and is, for example, in the range of 0.1 μm to 20 μm. As the Al source powder, any form can be used as long as it can be sulfided with hydrogen sulfide gas such as sulfide, oxide, carbonate and oxalate in addition to metal Al. As the Mn source powder, any form of metal Mn can be used as long as it can be sulfided with hydrogen sulfide gas, such as sulfide, oxide, carbonate, oxalate. The particle diameter of the Mn and Al source powder is, for example, in the range of 0.1 μm to 20 μm. Similarly, the co-additive source powder may be in any form as long as it can be sulfided with hydrogen sulfide gas, such as sulfide, oxide, carbonate, oxalate, etc., in addition to metal. The average diameter of the powder for co-additive source is, for example, in the range of 0.1 μm to 20 μm. For powder mixing, either a dry method or a wet method may be used. In the case of a dry method, for example, a ball mill may be used for pulverization and mixing.

Next, the obtained mixed powder is fired. Firing is performed, for example, by putting the above-described mixed powder into a quartz boat, heat-treating it in an electric furnace, and then rapidly cooling it. Usually, the heat treatment atmosphere is an inert gas atmosphere such as argon or a mixed atmosphere containing about 5 vol% of H ₂ S (hydrogen sulfide) gas. In normal cases, the firing temperature is about 600 ° C. to 1200 ° C., and preferably about 1000 ° C. to 1050 ° C. The firing time is, for example, about 30 minutes to 3 hours.

  The fired body obtained by the firing treatment may be used as it is, or may be used after pulverization.

  On the other hand, the red light emitting phosphor of the present invention can be provided as a thin film in addition to the powder.

  When the red light-emitting phosphor of the present invention is manufactured as a thin-film phosphor, this phosphor is a vapor deposition method including CVD (chemical vapor deposition), PVD (physical vapor deposition) and electron beam vapor deposition, Alternatively, it can be formed by sputtering or the like.

For example, when a red light-emitting phosphor using SrGa ₂ S ₄ as a base material, Al, Mn as a light emission center, and Ce as a co-additive is manufactured using a vapor deposition method, vapor deposition is performed. As a source, respective materials of metal Sr, Ga ₂ S ₃ , Al ₂ S ₃ , metal Mn, and CeCl ₃ are prepared. Next, the phosphor according to the present invention can be formed by depositing these evaporation sources on the substrate while maintaining the substrate temperature at 500 ° C. or higher. The thickness of the thin film can be freely adjusted by changing the deposition time.

In the case where a red light emitting phosphor in which SrGa ₂ S ₄ is used as a base material and Al, Mn as a light emission center, and Ce as a co-additive are added is manufactured by an electron beam evaporation method. Two types of evaporation sources are used: an evaporation source obtained by mixing SrS with a Mn compound and a Ce compound and pressure forming, and a Ga ₂ S ₃ evaporation source containing Al. That is, by simultaneously evaporating these evaporation sources and supplying them on a substrate maintained at a temperature of 500 ° C. or higher, the phosphor according to the present invention can be formed into a thin film. Also in this case, the thickness of the thin film can be freely adjusted by changing the deposition time.

  After film formation, as a post-heat treatment, lamp heating or laser heating may be performed in an inert gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen sulfide (for example, 5 vol%). This makes it possible to improve the characteristics of the thin film phosphor.

On the other hand, in the sputtering method, a mixed material obtained by adding Al, Mn, and the above-mentioned co-additive to the base material of M ^II M ₂ ^III S ₄ is used as a target. Argon gas or a mixed gas of argon gas and hydrogen sulfide gas (5 vol%) is used as a sputtering gas source. That is, a thin film phosphor is formed on a substrate by sputtering the sputtering gas at a gas pressure of 0.1 to several Pa on a substrate heated in a range of room temperature to about 600 ° C. The thickness of the thin film can be freely adjusted by changing the sputtering time. Thereafter, as post-heat treatment, lamp heating or laser heating may be performed in an inert gas atmosphere or a mixed gas atmosphere of an inert gas and hydrogen sulfide (for example, 5%). This makes it possible to improve the characteristics of the thin film phosphor.

  Such a phosphor according to the present invention can be used as a phosphor for a FED (field emission display) device, for example, as a light emitting phosphor in a red region.

  FIG. 1 shows an example of an FED apparatus to which the red light emitting phosphor of the present invention can be applied.

  The FED apparatus 100 shown in FIG. 1 has two glass substrates 10A and 10B arranged at a predetermined interval and substantially parallel to each other, and a vacuum chamber is provided between these glass substrates. Is formed.

  The cathode layer 20 and the cold cathode element 30 are laminated in this order on the inner surface (that is, the vacuum side surface) of one glass substrate 10A. The cold cathode element 30 includes a silicon substrate 60, an insulating layer 50 disposed on the silicon substrate 60, and a gate electrode 40 disposed on the insulating layer 50. The insulating layer 50 is provided with openings 80 at a predetermined periodic interval, and the insulating layer 50 and the gate electrode 40 are not present in the opening 80. Instead, a cone-shaped electron emitter 70 is formed in the opening 80 so that the tip protrudes from the height level position of the insulating layer 50. However, the tip of the electron emitter 70 is at a height level equivalent to the height level of the gate electrode 40 and does not protrude from the opening 80. The bottom surface of the electron emitter 70 is in contact with the surface of the silicon substrate 60.

  An anode layer 90 and a phosphor layer 120 are laminated in this order on the inner surface (that is, the vacuum side) of the other glass substrate 10B. The phosphor layer 120 includes three types of phosphors that emit light in the blue, green, and red regions, and these phosphors are arranged on the anode layer 90 in a regular arrangement, that is, corresponding to each pixel. Is installed.

  In the FED device 100 configured as described above, when a potential V1 is applied between the cathode layer 20 and the gate electrode 40, a strong electric field is generated at the tip of the electron emitter 70, and thereby, from the tip of the electron emitter 70. Electrons are emitted toward the glass substrate 10B.

  Further, a potential V2 is also applied between the anode layer 90 and the cathode layer 20, and the emitted electrons e are accelerated by the electric field generated by this potential V2, and emit light of each color of blue, green and red. It collides with the phosphor layer 120 provided with the phosphor shown. Due to this electron collision, the phosphor contained in the phosphor layer 120 emits light, and blue, green, and red light emission corresponding to each pixel is generated. Thus, a color image can be obtained.

Here, in the conventional FED device, the phosphor layer is a light emitting phosphor in each of the blue, green, and red regions, and M ^II M ₂ ^III S ₄ : Ce, M ^II M ₂ ^III S ₄ : Eu, respectively. (Where M ^II is any one of Mg, Ca, Sr, Ba, or a combination thereof, and M ^III is any one of Ga, In, or a combination thereof), and Y ₂ O ₃ : Eu or CaS: Eu.

  However, when the phosphor layer is composed of such a different material system of the host material, even if the phosphor layer is irradiated with the electron beam under the same conditions, the charge-up behavior of the phosphor is different. A phenomenon occurs in which the color balance shifts with time. Accordingly, it is necessary to appropriately monitor such a color balance shift and adjust the color balance shift. In addition, since the material system is different, the service life may be greatly different for each color phosphor. In such a case, even if the phosphor that emits light of a certain color is not deteriorated, the entire phosphor layer cannot be used due to the deterioration of one material, resulting in a short device life. Problems arise. Furthermore, it is necessary to individually adjust a plurality of materials when manufacturing the phosphor layer, which causes a problem that the manufacturing cost of the phosphor layer and further the phosphor of the FED device increases.

On the other hand, in the FED device of the present invention, the phosphor layer 120 has M ^II M ₂ ^III S ₄ : Ce and M ^II M ₂ ^III S as the light emitting phosphors in the blue, green and red regions, respectively. ₄ : Eu and M ^II M ₂ ^III S ₄ as base materials, Al and Mn were added thereto, and at least one element in Group IIIa of the periodic table was added as a co-additive Having a red-emitting phosphor (wherein M ^II is any one of Mg, Ca, Sr, Ba, or a combination thereof, and M ^III is any one of Ga, In, or a combination thereof) .

In this case, since the phosphor layers 120 for light emission of each color are made of the same base material, that is, a material of M ^II M ₂ ^III S ₄ system, the degree of charge-up of the phosphors of each color is almost equal. The lifetimes of the phosphors of the respective colors can be aligned at substantially the same time. Therefore, the problem of adjusting the color balance due to charge-up and the problem that the difference in the lifetime of each phosphor increases, which occurs in the phosphor device of the conventional FED device, are less likely to occur. Furthermore, when the phosphor layer 120 is manufactured, the phosphors for the three primary colors can be easily obtained by simply changing the elements to be added based on the same base material, thereby significantly reducing the manufacturing cost. it can.

  In the above-described example, the application example of the present invention has been described using the FED device including the red light-emitting phosphor according to the present invention in the phosphor layer as an example. However, it will be apparent to those skilled in the art that the red light-emitting phosphor according to the present invention can be applied to other display devices such as an ELD (electroluminescent display) device and a lighting device.

  As known to those skilled in the art, an ordinary ELD device includes a transparent electrode 220, an insulating layer 230, a phosphor layer 240, an insulating layer 250, and a metal electrode 260 on a transparent substrate 210 as shown in FIG. It is configured by stacking in this order. However, in the ELD device 200 according to the present invention, the red light emitting phosphor according to the present invention is installed in the phosphor layer 240. In the figure, 270 represents electroluminescent light emission.

Examples of the present invention will be described below.
Example 1
In Example 1, a phosphor containing SrGa ₂ S ₄ as a base material, containing Al and Mn as an emission center, and containing Ce as a co-additive was produced by the following method.

First, SrGa ₂ S ₄ powder having an average particle diameter of 1 μm (purity 99.99%, manufactured by High Purity Chemical Co., Ltd.) and AlF ₃ powder having an average particle diameter of 1 μm (purity 99.99%, high purity chemical). (Made by Co., Ltd.) 1 mol%, Mn metal powder having an average particle diameter of 1 μm (purity 99.99%, high-purity chemical Co., Ltd.) 6 mol%, and Ce ₂ S ₃ powder having an average particle diameter of 1 μm (99.9%, manufactured by High Purity Chemical Co., Ltd.) and 0.2 mol% were added and pulverized and stirred for 30 minutes with a mill mixer (model number 8000: manufactured by Specs) to obtain a mixed raw material powder. . Ce ₂ S ₃ powder was added so that the Ce concentration was 0.1 mol% with respect to the total amount of powder.

  Next, about 4 g of this mixed raw material powder was placed in a quartz boat and placed in an electric furnace. Next, the atmosphere in the electric furnace was changed to an argon + 5 vol% hydrogen sulfide atmosphere, the quartz boat was held at 1200 ° C. for 1 hour, and the mixed raw material powder was fired.

The obtained powder was pulverized to an average particle size of about 1 μm using a mortar to obtain a phosphor powder according to Example 1.
(Example 2)
In Example 2, a phosphor containing SrGa ₂ S ₄ as a base material, Al and Mn as a light emission center, and La as a co-additive was produced.

First, SrGa ₂ S ₄ powder having an average particle diameter of 1 μm (purity 99.99%, manufactured by High Purity Chemical Co., Ltd.) and AlF ₃ powder having an average particle diameter of 1 μm (purity 99.99%, high purity chemical). (Made by Co., Ltd.) 1 mol%, Mn powder with an average particle diameter of 1 μm (purity 99.99%, manufactured by High Purity Chemical Co., Ltd.) 6 mol%, and La ₂ S ₃ powder with an average particle diameter of 1 μm ( 99.9%, manufactured by High Purity Chemical Co., Ltd.) and pulverized and stirred in a mill mixer for 30 minutes to obtain a mixed raw material powder. The La ₂ S ₃ powder was added so that the La concentration was 0.1 mol% with respect to the total powder amount.

  Next, about 4 g of this mixed raw material powder was placed in a quartz boat and placed in an electric furnace. Next, the atmosphere in the electric furnace was changed to an argon + 5 vol% hydrogen sulfide atmosphere, the quartz boat was held at 1200 ° C. for 1 hour, and the mixed raw material powder was fired.

The obtained powder was pulverized to an average particle size of about 1 μm using a mortar to obtain a phosphor powder according to Example 2.
(Examples 3 to 15)
A phosphor containing SrGa ₂ S ₄ as a base material, Al and Mn as a light emission center, and further containing a co-additive R was produced by the same method as in Example 1 described above. However, the co-additive R was any of Gd, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Y, or Sc (referred to as Examples 3 to 15 respectively). The addition concentrations of Al, Mn, and co-additive R were 1 mol%, 6 mol%, and 0.1 mol%, respectively, with respect to the total amount of powder.
(Comparative Example 1)
In the same manner as in Example 1 described above, a phosphor containing SrGa ₂ S ₄ as a base material and containing Mn as an emission center was produced. In Comparative Example 1, only Mn (6 mol%) was added, and Al was not added. The co-additive was Ce (0.1 mol%).
(Comparative Example 2)
In the same manner as in Example 1, a phosphor containing ZnGa ₂ S ₄ as a base material and containing Mn as an emission center was produced. However, in this example, only Mn (6 mol%) was added as a dopant, and Al and a co-additive were not added.
(Characteristic evaluation of phosphor)
The powder phosphors of Examples 1 to 15 and Comparative Examples 1 and 2 manufactured by the method described above were irradiated with ultraviolet rays (wavelength: about 365 nm) to evaluate the light emission characteristics.

  FIG. 3 shows the emission peak of the phosphor according to Example 1 (A line). In this figure, the light emission characteristic of the phosphor according to Comparative Example 1 is simultaneously shown as B line, and the light emission characteristic of the phosphor according to Comparative Example 2 is simultaneously shown as C line. FIG. 4 shows the emission peak of the phosphor according to Example 2 (D line).

  As is clear from FIGS. 3 and 4, in the powdered phosphors according to Example 1 (A line) and Example 2 (D line), a red emission peak was obtained in a wavelength region of about 650 nm. The color coordinates (x, y) of these emission colors are about (0.69, 0.30). On the other hand, in the powdered phosphor according to Comparative Example 1, an emission peak was obtained at a wavelength of 700 nm.

  Further, the ratio of the integrated intensity of the phosphors according to Examples 1 and 2 to the integrated value of the emission intensity in the region of 600 nm to 800 nm in the background is 13 and 10, respectively, and Al, Mn It was also found that a very good red emission peak can be obtained by adding both the co-additive and the co-additive.

  Table 1 shows the emission peak wavelengths of the phosphors according to Examples 1 to 15. Further, in the table, each fluorescence according to Examples 1 to 15 with respect to the integrated value of the background emission intensity in the region of 600 nm to 800 nm of the phosphor according to Comparative Example 2 (that is, the phosphor not including the co-additive) is shown. Indicates the ratio of the integrated values of peak intensity in the same region of the body.

この表から、実施例１〜１５に係る蛍光体では、Ｍｎのみを添加した比較例２に係る蛍光体に比べて、赤色領域の発光が１．２倍から４５倍も増大していることがわかる。このように、ＡｌおよびＭｎとともに第ＩＩＩａ族元素を０．１ｍｏｌ％添加した蛍光体では、波長約６５０nmの領域に、バックグラウンドピークを越える有意な発光ピークが得られることがわかった。

From this table, in the phosphors according to Examples 1 to 15, the emission in the red region is increased by 1.2 to 45 times compared to the phosphor according to Comparative Example 2 in which only Mn is added. Recognize. Thus, it was found that a phosphor having 0.1 mol% of the Group IIIa element added together with Al and Mn has a significant emission peak exceeding the background peak in the wavelength region of about 650 nm.

  The red light-emitting phosphor of the present invention emits light by irradiating the phosphor with an excitation energy source such as an electron beam, ultraviolet light, X-rays, and an electric field. Can be used as

It is an example of the FED apparatus with which the red light emission fluorescent substance which concerns on this invention was installed as a part of fluorescent substance layer. It is an example of the ELD device in which the red light emitting phosphor according to the present invention is installed as a part of the light emitting layer. It is a figure which shows the light emission peak of the red light emission fluorescent substance (Example 1) which concerns on this invention. It is a figure which shows the light emission peak of another red light emission fluorescent substance (Example 2) which concerns on this invention.

Explanation of symbols

10A, 10B Glass substrate 20 Cathode layer 30 Cold cathode element 40 Gate electrode 50 Insulating layer 60 Silicon substrate 70 Electron emitter 80 Opening 90 Anode layer 100 FED device 120 Phosphor layer 200 ELD device 210 Transparent substrate 220 Transparent electrode 230 Insulating layer 240 Phosphor layer 250 Insulating layer 260 Metal electrode A Luminescent property of phosphor material according to Example 1 B Luminescent property of phosphor material according to Comparative Example C C Luminescent property of phosphor material according to Comparative Example D D In Example 2 Luminescent characteristics of the phosphor material.

Claims (4)

M ^II M ₂ ^III S ₄ (where M ^II is any one of Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), or a combination thereof, and M ^III is Ga Al (aluminum) and Mn (manganese) are added to a base material represented by (gallium), In (indium), or a combination thereof, and further, Group IIIa of the periodic table of elements A red light emitting phosphor in which at least one element is added as a co-additive.   The co-additives are Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium). 2. The red color according to claim 1, comprising at least one of Er, Er (erbium), Tm (thulium), Yb (ytterbium), Y (yttrium), Sc (scandium), and La (lanthanum). Luminescent phosphor. A cold cathode device installed on the cathode layer and having a plurality of electron emitters installed in the opening; and
An anode provided with a phosphor layer on the side facing the cold cathode element;
Have
A field emission display (FED) device in which a phosphor emits light by electrons emitted from the cold cathode device,
The FED device according to claim 1, wherein the phosphor layer includes the red light-emitting phosphor according to claim 1. An electroluminescent display (ELD) device having an insulating layer on one side or both sides of a phosphor layer and further having electrodes to which a voltage can be applied on both sides of the insulating layer,
The ELD device according to claim 1, wherein the phosphor layer includes the red light-emitting phosphor according to claim 1.

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